JP5554928B2 - Coating method for enhancing electromigration resistance of copper - Google Patents

Description

The present invention generally provides methods and compositions for limiting copper surface diffusion, particularly electromigration, i.e., under an electric field, during operation of a semiconductor device by improving the adhesion strength between copper and an etch stop layer (ESL). Related to things.

Copper is widely used to form the multilayer wiring required in today's ultra-large scale integrated circuit (ULSI) semiconductor devices because of its lower resistivity and improved electromigration resistance compared to aluminum. It has come to be.

Multilayer wiring forms a network of copper wiring (formed in trenches) that is used to route various signals in addition to power and ground to various regions of the integrated circuit. To further increase area efficiency, these interconnects are stacked to form several layers separated by a dielectric material, and each layer is connected to each other through vertical openings called vias.

The wiring and the via are usually formed using a damascene process sequence (see, for example, Non-Patent Document 1). In the damascene process sequence, at each layer of the wiring system, features are etched into the dielectric material and then filled with copper before planarization. The above sequence can be simplified and explained as follows.
• Dry etch the dielectric material to form trenches and / or vias.
Deposit a Cu diffusion barrier (usually TaN / Ta) (conventional physical vapor deposition: deposited by PVD). This is because copper diffuses quickly in the dielectric and reaches the underlying transistor in silicon, leading to device failure.
Conventionally, a copper “seed layer” is deposited by PVD.
Electrochemically deposit copper to fill vias and trenches.
Planarization is performed by chemical mechanical polishing (CMP) so that copper wiring is embedded. That is, the surface of copper is set to the same height as the surface of the surrounding dielectric.
A dielectric encapsulation layer that serves as a copper diffusion barrier and also as an etch stop layer (ESL) during patterning and etching of the overlying inter-metal dielectric material [Usually SiCN, SiN, SiC, SiOCN, or SiON deposited by plasma enhanced chemical vapor deposition (PECVD)] is deposited on the embedded copper wiring.
Deposit the next layer of intermetallic dielectric material (usually a material with a low dielectric constant, such as less than 4.0).

The higher the device integration density, the smaller the width of wiring, vias and other irregularities on the circuit. As a result, the cross-sectional areas of the wiring and vias are reduced and the current density transmitted in the copper wiring is increased.

The electromigration phenomenon in copper interconnects is strengthened by increasing the current density. Electromigration is described as the movement of metal atoms in the interconnects in the direction of current flow.

As a result of the movement of copper atoms, vacancies, and therefore voids, are formed in certain areas of the copper wiring, resulting in reliability problems that eventually cause the wiring system and then the integrated circuit itself to fail completely. End up.

In copper wiring, since the surface diffusion coefficient of copper is larger than its self-diffusion coefficient, it has been shown that electromigration mainly proceeds by surface diffusion of copper atoms or copper ions (for example, see Non-Patent Document 2). ). The surface diffusion of copper occurs preferentially along the most fragile interface of the copper wiring (wherein the copper atoms are weakly bonded so that the copper atoms move relatively easily).

In the copper wiring, the most fragile interface is the upper surface of the wiring in contact with the ESL (see, for example, Non-Patent Document 3).

Therefore, it is desired to increase the adhesion strength between copper and ESL, limit the copper surface diffusion, and improve the electromigration resistance and the reliability of the wiring system.

Several techniques for improving the adhesion between ESL and copper and the resistance to electromigration have been proposed.

Plasma treatment is used to reduce gas bodies such as ammonia and hydrogen (see, for example, Patent Documents 1, 2, and 3), thereby reducing copper oxide and other contamination present on the copper surface. Since the substance can be removed, the adhesion of ESL is improved. However, due to the physical and directional nature of the above treatment, some copper sputtering film is formed on the surrounding dielectric region, increasing the risk of electrical leakage between wires. Some copper on the top surface is removed during the above process, which increases the wiring resistance which degrades the interconnect performance.

Silicidation of the copper surface has been proposed to improve adhesion with Si-based ESL (see, for example, Patent Documents 4, 5, and 6). During the silicidation process, some copper is consumed from the interconnect to form a more resistive copper silicide. In this way, the wiring resistance is also increased.

Doping copper with other metals, such as Ag or Zr, in the bulk of the wiring during the electrochemical filling step, or only on the top surface of the copper wiring, is also suggested to increase resistance to electromigration. (For example, see Patent Documents 7 and 8). In this case, the dopant will function as a physical copper diffusion blocker, or will aid in forming larger copper particles and eliminate the copper diffusion path.

Again, the use of dopants with lower electrical conductivity compared to copper will increase the wiring resistance.

It has also been proposed to use a selective and conductive cap layer on the copper interconnect, such as a CoWP layer deposited by an electroless deposition process (see, for example, Patent Documents 9, 10, and 11). In this case, copper surface diffusion is limited by intermetallic bonding. Such a cap layer can also be provided with a copper diffusion barrier, thus theoretically eliminating the need for a SiCN layer.

However, integrating them in a dual damascene process sequence without using ESL is not easy, especially when via misalignment must be taken into account.

Furthermore, it is very difficult to maintain deposition selectivity when the wiring density increases. In this way, leakage between the wirings increases, and in some cases, a short circuit occurs between the wirings.

In order to improve the reliability of ULSI devices by increasing the resistance to wiring electromigration and to alleviate the above limitations in the prior art, the following methods: (1) Upper surface diffusion of copper atoms or copper ions in copper wiring (2) Improve the copper / ESL interface by increasing its adhesion strength and electromigration resistance, and (3) improve electrical characteristics of the wiring system, especially wiring resistance and leakage between wiring There is a need for a method that can be maintained.
US Pat. No. 6,946,401 US Pat. No. 6,764,952 US Pat. No. 6,593,660 US Pat. No. 6,492,266 US Pat. No. 6,977,218 US Pat. No. 5,447,877 US Pat. No. 6,387,806 US Pat. No. 6,268,291 US Pat. No. 6,893,959 US Pat. No. 6,902,605 US Patent Application Publication No. 2005/0266673 S. Wolf: “Silicon processing for the VLSI Era”, Vol. 4, p. 671-687 C. K. Hu et al. , Microelectronics and Reliability, Vol.46, Issues 2-4, p.213-231. T. T. et al. C. Wang et al. , Thin Solid Films, 498 (2006) p.36-42.

The present invention addresses the above-described problem of lack of device reliability due to copper electromigration at the upper surface of the interconnect in the interconnect using a new approach.

In accordance with the present invention, a non-conductive (dielectric) cap layer can be formed by chemical or mechanical grafting using a specific or covalent grafting process without chemical electroless deposition steps using some specific compounds. It was confirmed that it can be formed on a wire or a copper alloy wire.

The main purpose of this cap layer is to improve the quality of the copper-etch stop layer (ESL) / diffusion barrier interface.

The non-conductivity of the cap layer of the present invention provides the possibility of depositing it selectively on copper wiring or non-selectively on the entire wafer surface.

Therefore, according to the first aspect, the present invention provides:
A method for producing a multilayer composite device such as a semiconductor device,
(A) The surface of the composite material a)
-Diazonium salt of aniline;
A diazonium salt carrying at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group; or a precursor of the diazonium salt;
Formula: H ₂ N—A—X—Z
[Where:
A is an aryl group which may be substituted or unsubstituted with a hydroxyl group, a lower alkyl group or a halogen atom, preferably a phenyl group; —CH—X—B group (wherein
B is an aryl or heteroaryl group, preferably a phenyl group or a 5- or 6-membered heteroaryl group having 1 to 3 nitrogen atoms)
Selected from the group consisting of
X is a single bond or an alkylene group having 1 to 4 carbon atoms, preferably a —CH ₂ — group or a —CH ₂ —CH ₂ — group,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group, preferably an amine group or a carboxyl group]
In a solution containing the amine compound of
b) or
Following the first solution containing the aryldiazonium salt,
An aryl radical carrying at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group, and grafted to the surface of the composite material by the first solution A second solution containing a compound bearing at least one functional group capable of reacting with
By contacting,
Forming a dielectric layer on the surface of the composite material having at least one region made of a dielectric material and at least one region made of copper or a copper alloy;
(B) A step of forming an upper layer on the surface of the composite material obtained in step (A), wherein the upper layer is a Si-containing dielectric Cu etching stop layer (Si-containing dielectric Cu-Etch). And a step comprising a copper diffusion barrier.

Unexpectedly, by the diazonium salt of aniline, as well as the diazonium salt and amine compound defined above,
i) Spontaneous reaction with metallic copper, ie a strong interaction (in short, graft) is shown, the Cu or Cu alloy interface is stabilized with respect to electromigration,
ii) It has been found that the compatibility with subsequent process steps is increased, and in particular the adhesion to the Si-containing copper or copper alloy diffusion barrier and / or etch stop layer, which is PECVD deposited, is very good.

Furthermore, these compounds show good thermal stability and can be reliably integrated with subsequent steps.

Thus, the uniqueness of the present invention is that it improves the adhesion between copper and ESL to ensure good electromigration resistance and is one or more as defined above which is a precursor of a non-conductive cap layer. It is in the use of a novel solution containing a specific compound.

As used herein, the term “lower alkyl group” is understood to mean a straight or branched hydrocarbon chain having 1 to 4 carbon atoms. Such an alkyl group is, for example, a methyl group, an ethyl group, a propyl group, or a 1-methyl-ethyl group, preferably a methyl group.

The term “alkylene group having 1 to 4 carbon atoms” refers to a straight chain divalent hydrocarbon of the formula: — (CH ₂ ) _n —, where n is 1, 2, 3, or 4. A branched or divalent hydrocarbon chain having 1 to 4 carbon atoms (for example, —CH (CH ₃ ) —, —CH (CH ₃ ) —CH ₂ —, —CH (CH ₃ ) —CH ₂ -CH ₂ -, or _{-C (CH 3) 2 -CH 2} - is understood to mean, etc.).

The term “halogen atom” is understood to mean a fluorine atom, a chlorine atom or a bromine atom, preferably a fluorine atom or a chlorine atom.

The diazonium salt of aniline has the following formula:

It is understood to mean

In the present invention, the layer is deposited by dipping, spraying or spin-coating the wafer surface with one or two solutions containing one or more precursors of a dielectric (ie, cap) layer. Is advantageous.

Depending on the solution composition chosen, the cap layer can be deposited selectively on the copper or copper alloy wiring or non-selectively on the surface of the copper or copper alloy and dielectric.

After exposure to the solution, the wafer surface may be washed with deionized water or isopropyl alcohol and dried before proceeding with a standard ESL deposition process.

The resulting cap layer exhibits good heat and plasma resistance, ensuring compatibility with ESL deposition.

The solution composition of the present invention, and in particular the concentration of the precursor, is preferably less than 15 nm, more preferably less than 10 nm, more preferably less than 10 nm, so that the effect on the dielectric permittivity of the stack is minimized. More advantageously it will be less than 8 nm, even more advantageously 1-8 nm. Such concentrations will vary depending on the chemical nature of the compound used, but can be readily determined by one skilled in the art.

According to a first embodiment of the invention, the surface of a composite material having at least one region made of a dielectric material and at least one region made of copper or a copper alloy is formed by Cu Or one solution containing a compound that stabilizes the Cu alloy interface with respect to electromigration and PECVD deposited, and that provides very good adhesion to Si-containing copper or copper alloy diffusion barriers and / or etch stop layers, Contact is preferably made with an aqueous solution, preferably by dipping, spraying or spin coating.

According to one particular embodiment, the compound is a diazonium salt of aniline, which can be generated in situ or pre-synthesized. Excellent results were obtained in an aqueous solution containing the diazonium salt of aniline produced in situ at a concentration of 5-50 mM, preferably about 10 mM, so as to obtain a cap layer of 1-8 nm.

According to another particular embodiment, the compound is a diazonium salt bearing at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group. These functional groups have been confirmed to provide excellent adhesion to Si-containing copper or copper alloy diffusion barriers and / or etch stop layers deposited by PECVD.

These diazonium salts can be generated in situ or synthesized beforehand. When the diazonium salt is generated in situ, the preparation of the diazonium salt of aniline includes, for example, a mixture of sodium nitrite, isoamyl nitrite and tetrafluoroborohydride, potassium nitrite, nitrosyl tetrafluoroborate The diazotization can proceed by using any nitrosyl or nitrous acid derivative, such as (nitrosytetrafluoroborate), nitrosylsulfate.

In the construction of the present invention, the preferred diazonium salt is of the formula: N≡NDXZ
(Where
D is an aryl group, preferably a phenyl group, which may be substituted or unsubstituted with a hydroxyl group, a lower alkyl group or a halogen atom,
X is a single bond or an alkylene group having 1 to 4 carbon atoms, preferably a —CH ₂ — group or a —CH ₂ —CH ₂ — group,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group, preferably an amine group or a carboxyl group)
It is a compound of this.

The diazonium salt has the formula N≡NDXZ
(Where
D is a phenyl group,
(X is an alkylene group having 1 to 4 carbon atoms, preferably a —CH ₂ — group or a —CH ₂ —CH ₂ — group, and Z is a carboxyl group)
Particularly preferred is a diazonium salt of phenylalkanoic acid having

Excellent results were obtained with the following solutions.
An aqueous solution containing 4-diazophenylacetic acid generated from 4-aminophenylacetic acid and sodium nitrite in situ at a concentration of 5 to 50 mM, preferably about 10 mM, so as to obtain a cap layer of 1 to 8 nm.
5 to 50 mM, preferably 5 to 50 mM, of 4- (2-aminoethyl) phenyldiazonium salt generated from 4- (2-aminoethyl) aniline and sodium nitrite on site to obtain a 1-8 nm cap layer Is an aqueous solution containing about 10 mM.
An aqueous solution containing 4-diazophenyl acetic acid tetrafluoroborate synthesized in advance at a concentration of 5 to 50 mM, preferably about 10 mM, so as to obtain a cap layer of 1 to 8 nm.

According to another particular embodiment, said compound is an amine compound of the formula: H ₂ N—A—X—Z as defined above.

In the configuration of the present invention, a preferred amine compound is represented by the formula: H ₂ N—A—X—Z
[Where:
A is a —CH—X—B group (wherein B is a phenyl group or a 5- or 6-membered heteroaryl group having 1 to 3 nitrogen atoms, preferably an imidazolyl group)
And
X is a single bond, or a —CH ₂ — group or —CH ₂ —CH ₂ — group,
・ Z is a carboxyl group]
It is a compound of this.

Excellent results were obtained with the following solutions.
An aqueous solution containing histidine at a concentration of 5 to 50 mM, preferably about 10 mM, so that a cap layer of 1 to 8 nm is obtained.
An aqueous solution containing 3-amino-3-phenylpropionic acid at a concentration of 5 to 50 mM, preferably about 10 mM, so that a cap layer of 1 to 8 nm is obtained.

According to a second embodiment of the present invention, the surface of the composite material having at least one region made of a dielectric material and at least one region made of copper or a copper alloy contains an aryldiazonium salt Followed by a first solution, preferably an aqueous solution, carrying at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group, and the aryldiazonium salt as described above. The second solution containing a compound bearing at least one functional group capable of reacting with an aryl radical grafted on the surface of the composite material is contacted, preferably by dipping, spraying or spin coating.

According to one particular embodiment, the aryldiazonium salt has the formula N≡NDXZ
(Where
D is an aryl group, preferably a phenyl group, which may be substituted or unsubstituted with a hydroxyl group, a lower alkyl group or a halogen atom,
X is a single bond or an alkylene group having 1 to 4 carbon atoms, preferably a —CH ₂ — group or a —CH ₂ —CH ₂ — group,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group, preferably an amine group or a carboxyl group)
It is a compound of this.

As described above with respect to the first embodiment of the invention, these diazonium salts can be generated in situ or can be pre-synthesized.

According to another particular embodiment, said compound bearing at least one functional group of said second solution is polysilazane.

Excellent results were obtained with the following solutions.
A first aqueous solution of 4-diazosalicylic acid generated in situ from 4-aminosalicylic acid and sodium nitrite.
A second solution that causes a conventional peptide binding reaction between a silazane derivative (KION® Cerase® 20 polysilazane) and a diazonium salt.

After exposure to the solution of the present invention, the surface of the composite may be washed and dried, for example with deionized water or isopropyl alcohol, before proceeding to a standard ESL deposition process and / or copper diffusion barrier deposition. It is advantageous.

In this respect, the process of the present invention can be used not only with PECVD SiCN, the industry standard for ESL / barriers, but also with SiN, SiC, SiOCN, or SiON, as well as with known types of Cu diffusion barriers. It is noted.

In the method according to the present invention, the dielectric layer or cap layer is preferably formed after chemical mechanical polishing (CMP) and after cleaning. Alternatively, the layer can be formed during chemical mechanical polishing (CMP) or during cleaning performed after CMP.

In a preferred embodiment of the present invention, the composite material is coated with a silicon dioxide layer or Si-containing low-k dielectric layer deposited by plasma enhanced chemical vapor deposition (PECVD), including copper or copper alloy wiring. Made of silicon material.

More preferably, the composite material is a semiconductor device, particularly an integrated circuit multilayer wiring system.

According to a second aspect, the present invention relates to a multilayer composite device obtainable by the above method.

Thus, the device according to the present invention generally comprises a dielectric layer grafted on the surface of a copper or copper alloy region of a composite material, the dielectric layer and the dielectric region of the composite material being a dielectric Cu etch stop layer. And / or coated with a copper diffusion barrier.

More specifically, the semiconductor device is
A dielectric layer having one or more trenches;
A copper wiring formed in the trench;
A cap layer formed on the copper wiring so formed and covered with an upper layer composed of a Si-containing dielectric Cu etch stop layer and / or a copper diffusion barrier;
A silicon dioxide layer or a Si-containing low-k dielectric layer formed on the etch stop layer and / or the copper diffusion barrier.

The thickness of the dielectric capping layer is preferably less than 15 nm, more preferably less than 10 nm, even more preferably less than 8 nm, even more preferably 1 to 8 nm.

According to a third aspect, the present invention relates to a solution used to form a dielectric cap layer in the above method.

The solution comprises a solvent, preferably water or a mixture of water and a water-soluble alcohol, and at least one compound selected from the group consisting of a diazonium salt of aniline, a diazonium salt as defined above, and an amine compound. The cap layer is preferably contained in a concentration sufficient to obtain a thickness of less than 15 nm, more preferably less than 10 nm, even more preferably less than 8 nm, and even more preferably 1-8 nm.

Advantageously, the solution further contains an acid such as sulfuric acid.

In the following, the present invention will be explained by the following examples of producing a copper wiring structure for a semiconductor device using the method according to the present invention. However, the present invention is not limited to the following examples.

Note that in these examples, the bath composition includes only water and the cap layer precursor. Needless to say, another additive may be further added.

Example 1
The substrate used in this example consisted of a silicon material coated with a 400 nm layer of silicon dioxide deposited by plasma enhanced chemical vapor deposition (PECVD). A tantalum nitride (TaN) layer having a thickness of 15 nm is deposited on the silicon dioxide layer by physical vapor deposition (PVD), and a tantalum (Ta) layer having a thickness of 10 nm is similarly deposited on the layer by PVD. A silicon dioxide layer was coated. A 100 nm copper seed layer was deposited on the Ta layer by PVD, and a 1 μm copper layer was electrochemically deposited on the copper seed layer.

Next, chemical mechanical polishing (CMP) was applied to the substrate surface to reduce the total copper thickness to 500 nm.

The substrate was cleaned by first immersing in a solution containing 0.1% by weight sulfuric acid for 30 seconds and then in a solution containing 2.5% by weight citric acid for 10 seconds.

The substrate was then washed with deionized water (DIW) and dried with nitrogen.

The substrate was then coated using the solution of the present invention (see coating protocol below).

The properties of the coating were determined by Fourier transform infrared (FT-IRRAS) spectroscopy.

After coating the substrate using the solution of the present invention, an 80 nm thick silicon nitride (SiN) layer was deposited on the substrate by PECVD using silane (SiH ₄ ) / ammonia (NH ₃ ) chemistry.

The adhesion of the SiN layer on the copper was evaluated by measuring the critical point of the force to delaminate the SiN layer in the micro scratch test.

The solution of the present invention in this particular example was an aqueous sulfuric acid (0.01N) solution containing 0.93 grams / liter (10 mM) aniline and 0.7 grams / liter (10 mM) sodium nitrite. It was.

Coating protocol After the substrate was cleaned by the above procedure, the substrate was immersed in the solution of the present invention for 10 minutes while applying ultrasonic vibration. The substrate was then washed with ethanol, then with DIW, then with acetone and dried with nitrogen.

result
FT-IRRAS characteristics The table below shows the various transmission bands of the coated thin films.

The corresponding band shows the properties of the aniline molecule.

Adhesion When using the coating of the present invention, the adhesion of SiN on copper was improved by 10% compared to the state where the copper surface was not coated.

Electrical Results The above process was performed on a patterned substrate in which copper wiring was embedded in SiO2 and the electrical performance evaluation structure known to those skilled in the art was designed. After processing, an 80 nm SiN layer was deposited on the substrate, and then the substrate was passivated in the same procedure as during actual integrated circuit fabrication.

The treated structure and the untreated structure were evaluated for electrical continuity, wiring leakage and wiring resistance. From this evaluation, it was found that the structure treated as described above exhibited the same performance as the untreated structure.

Reliability results After electrical evaluation, the structures used above, i.e. both processed and unprocessed, were separated into different chips and packaged by procedures known to those skilled in the art. An electromigration test was performed on the packaged chip. The life of the treated chip was significantly longer than that of the untreated chip.

Example 2
The substrate used in this example consisted of a silicon material coated with a 400 nm layer of silicon dioxide deposited by plasma enhanced chemical vapor deposition (PECVD). A tantalum nitride (TaN) layer having a thickness of 15 nm is deposited on the silicon dioxide layer by physical vapor deposition (PVD), and a tantalum (Ta) layer having a thickness of 10 nm is similarly deposited on the layer by PVD. A silicon dioxide layer was coated. A 100 nm copper seed layer was deposited on the Ta layer by PVD, and a 1 μm copper layer was electrochemically deposited on the copper seed layer.

Next, chemical mechanical polishing (CMP) was applied to the substrate surface to reduce the total thickness of copper to 500 nm.

The substrate was cleaned by first immersing in a solution containing 0.1% by weight sulfuric acid for 30 seconds and then by immersing in a solution containing 2.5% by weight citric acid for 1 minute.

The substrate was then washed with deionized water (DIW) and dried with nitrogen.

The substrate was then coated using the solution of the present invention (see coating protocol below).

The properties of the coating were determined by Fourier transform infrared (FT-IRRAS) spectroscopy, time-of-flight secondary ion mass (TOF-SIMS) analysis.

After coating the substrate using the solution of the present invention, an 80 nm thick silicon nitride (SiN) layer was deposited on the substrate by PECVD using silane (SiH ₄ ) / ammonia (NH ₃ ) chemistry.

The adhesion of the SiN layer on the copper was evaluated by measuring the critical point of the force to delaminate the SiN layer in the micro scratch test.

The solution of the present invention in this particular example is sulfuric acid (0.01 N) containing 1.52 grams / liter (10 mM) of 4-aminophenylacetic acid and 0.7 grams / liter (10 mM) of sodium nitrite. ) Aqueous solution.

Coating protocol After the substrate was cleaned by the above procedure, the substrate was immersed in the chemical solution of the present invention for 10 minutes while applying ultrasonic vibration. The substrate was then washed with ethanol, then with DIW, then with acetone and dried with nitrogen.

result
FT-IRRAS characteristics The table below shows the various transmission bands of the coated thin films.

The corresponding band shows the properties of the 4-aminophenylacetic acid molecule.

TOF-SIMS
According to the TOF-SIMS analysis method, the following peaks are attributed to the coated thin film.

Adhesion When using the coating of the present invention, the adhesion of SiN on copper was improved by 64% compared to the state where the copper surface was not coated.

Example 3
The substrate used in this example consisted of a silicon material coated with a 400 nm layer of silicon dioxide deposited by plasma enhanced chemical vapor deposition (PECVD). A tantalum nitride (TaN) layer having a thickness of 15 nm is deposited on the silicon dioxide layer by physical vapor deposition (PVD), and a tantalum (Ta) layer having a thickness of 10 nm is similarly deposited on the layer by PVD. A silicon dioxide layer was coated. A 100 nm copper seed layer was deposited on the Ta layer by PVD, and a 1 μm copper layer was electrochemically deposited on the copper seed layer.

Next, chemical mechanical polishing (CMP) was applied to the substrate surface to reduce the total copper thickness to 500 nm.

The substrate was cleaned by first immersing in a solution containing 0.1% by weight sulfuric acid for 30 seconds and then by immersing in a solution containing 2.5% by weight citric acid for 1 minute.

The substrate was then washed with deionized water (DIW) and dried with nitrogen.

The substrate was then coated using the solution of the present invention (see coating protocol below).

The properties of the coating were determined by Fourier transform infrared (FT-IRRAS) spectroscopy, time-of-flight secondary ion mass (TOF-SIMS) analysis.

After coating the substrate using the solution of the present invention, an 80 nm thick silicon nitride (SiN) layer was deposited on the substrate by PECVD using silane (SiH ₄ ) / ammonia (NH ₃ ) chemistry.

The adhesion of the SiN layer on the copper was evaluated by measuring the critical point of the force to delaminate the SiN layer in the micro scratch test.

The solution of the present invention in this particular example was sulfuric acid containing 1.4 milliliters / liter (10 mM) 4- (2-aminoethyl) aniline and 0.7 grams / liter (10 mM) sodium nitrite. (0.01N) aqueous solution.

Coating protocol After the substrate was cleaned by the above procedure, the substrate was immersed in the solution of the present invention for 10 minutes while applying ultrasonic vibration. The substrate was then washed with ethanol, then with DIW, then with acetone and dried with nitrogen.

result
FT-IRRAS characteristics The table below shows the various transmission bands of the coated thin films.

The corresponding band shows the properties of the 4- (2-aminoethyl) aniline molecule.

TOF-SIMS
According to the TOF-SIMS analysis method, the following peaks are attributed to the coated thin film.

Adhesion When using the coating of the present invention, the adhesion of SiN on copper was improved by 64% compared to the state where the copper surface was not coated.

Example 4
The substrate used in this example consisted of a silicon material coated with a 400 nm layer of silicon dioxide deposited by plasma enhanced chemical vapor deposition (PECVD). A tantalum nitride (TaN) layer having a thickness of 15 nm is deposited on the silicon dioxide layer by physical vapor deposition (PVD), and a tantalum (Ta) layer having a thickness of 10 nm is similarly deposited on the layer by PVD. A silicon dioxide layer was coated. A 100 nm copper seed layer was deposited on the Ta layer by PVD, and a 1 μm copper layer was electrochemically deposited on the copper seed layer.

Next, chemical mechanical polishing (CMP) was applied to the substrate surface to reduce the total copper thickness to 500 nm.

The substrate was cleaned by first immersing in a solution containing 0.1% by weight sulfuric acid for 30 seconds and then by immersing in a solution containing 2.5% by weight citric acid for 1 minute.

The substrate was then washed with deionized water (DIW) and dried with nitrogen.

The substrate was then coated using the solution of the present invention (see coating protocol below).

The properties of the coating were determined by Fourier transform infrared (FT-IRRAS) spectroscopy, time-of-flight secondary ion mass (TOF-SIMS) analysis.

After coating the substrate using the solution of the present invention, an 80 nm thick silicon nitride (SiN) layer was deposited on the substrate by PECVD using silane (SiH ₄ ) / ammonia (NH ₃ ) chemistry.

The adhesion of the SiN layer on the copper was evaluated by measuring the critical point of the force to delaminate the SiN layer in the micro scratch test.

The solution of the present invention in this particular example was an aqueous sulfuric acid (0.01 N) solution containing 2.2 grams / liter (10 mM) of 4- (diazo) phenylacetic acid tetrafluoroborate.

Coating protocol After the substrate was cleaned by the above procedure, the substrate was immersed in the solution of the present invention for 10 minutes while applying ultrasonic vibration. The substrate was then washed with ethanol, then with DIW, then with acetone and dried with nitrogen.

result
FT-IRRAS characteristics The table below shows the various transmission bands of the coated thin films.

The corresponding band shows the properties of the 4- (diazo) phenylacetic acid tetrafluoroborate molecule.

TOF-SIMS
According to the TOF-SIMS analysis method, the following peaks are attributed to the coated thin film.

Adhesion When using the coating of the present invention, the adhesion of SiN on copper was improved by 10% compared to the state where the copper surface was not coated.

Example 5
The substrate used in this example consisted of a silicon material coated with a 400 nm layer of silicon dioxide deposited by plasma enhanced chemical vapor deposition (PECVD). A tantalum nitride (TaN) layer having a thickness of 15 nm is deposited on the silicon dioxide layer by physical vapor deposition (PVD), and a tantalum (Ta) layer having a thickness of 10 nm is similarly deposited on the layer by PVD. A silicon dioxide layer was coated. A 100 nm copper seed layer was deposited on the Ta layer by PVD, and a 1 μm copper layer was electrochemically deposited on the copper seed layer.

Next, chemical mechanical polishing (CMP) was applied to the substrate surface to reduce the total thickness of copper to 500 nm.

The substrate was cleaned by first immersing in a solution containing 0.1% by weight sulfuric acid for 30 seconds and then by immersing in a solution containing 2.5% by weight citric acid for 1 minute.

The substrate was then washed with deionized water (DIW) and dried with nitrogen.

The substrate was then coated in two steps, each using a specific solution (see coating protocol below).

The properties of the coating were determined by Fourier transform infrared (FT-IRRAS) spectroscopy.

After coating the substrate using the solution of the present invention, an 80 nm thick silicon nitride (SiN) layer was deposited on the substrate by PECVD using silane (SiH ₄ ) / ammonia (NH ₃ ) chemistry.

The adhesion of the SiN layer on the copper was measured by a 4-point bend technique.

In this particular example, two solutions were used in succession to coat the cleaned substrate.

The first solution used in this particular example was sulfuric acid (0.01 N) containing 1.54 grams / liter (10 mM) 4-aminosalicylic acid and 0.7 grams / liter (10 mM) sodium nitrite. ) Aqueous solution.

The second solution used in this particular example uses N, N′-dimethylformamide (DMF) as the solvent and 43.2 grams / liter (0.3 M) of N-hydroxybenzotriazole (HOBt) and 52 ml / liter (0.3 M) N, N′-diisopropylamine, 50 ml / liter (0.3 M) N, N′-diisopropylcarbodiimide (DIPCDI), and 20 grams / liter KION (registered) Trademark) Ceraset® 20 polysilazane.

Coating protocol
Step 1
After cleaning the substrate by the above procedure, the substrate was immersed in the first solution for 10 minutes while applying ultrasonic vibration. The substrate was then washed with ethanol and then with DIW, then with acetone and dried with nitrogen.

Step 2
After performing step 1 by the above procedure, the substrate was immersed in the second solution for 30 minutes while applying ultrasonic vibration. The substrate was then washed with DMF, then with DIW, then with acetone and dried with nitrogen.

result
FT-IRRAS characteristics The table below represents the various transmission bands shown on the substrate after step 1 of the coating protocol.

The corresponding band shows the properties of the 4-aminosalicylic acid molecule.

The table below represents the various transmission bands shown on the substrate after step 2 of the coating protocol.

Corresponding bands show the properties of 4-aminosalicylic acid molecules and silazane molecules.

Adhesion When using the coating of the present invention, the adhesion of SiN on copper was improved by 60% compared to the state where the copper surface was not coated.

Examples 6 and 7
According to the protocol of Example 1, an aqueous histidine solution and an aqueous 3-amino-3-phenylpropionic acid solution were tested.

The results thus obtained are summarized in the table below.

As can be seen from the above description and examples, the novel solution according to the present invention can provide a dielectric cap layer that improves the adhesion between copper and ESL and ensures good electromigration resistance.

Claims (20)

A method for producing a multilayer composite device comprising:
(A) a surface of the double coupling material having at least one region of at least one region of copper or a copper alloy made of a dielectric material)
Diazonium salt of aniline;
A diazonium salt carrying at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group; or a precursor of a diazonium salt carrying said at least one functional group ; And the formula: H ₂ N—A—X—Z
[Where:
A is an aryl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) , or a —CH—X—B group (wherein B is an aryl group or a heteroaryl group) . ,
X is a single bond or an alkylene group having 1 to 4 carbon atoms,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group]
Contacting with a solution comprising at least one compound selected from the group consisting of:
Or
b)
Following the first solution containing the aryldiazonium salt,
An aryl radical carrying at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group, and grafted to the surface of the composite material by the aryldiazonium salt; by letting come in contact in a second solution containing a compound bearing capable of reacting at least one functional group,
Forming on said surface before Symbol composite dielectric layer,
(B) obtained in step (A), directly on the front surface of the dielectric layer, and forming a top layer, dielectric Cu etch stop layer of the upper layer Si-containing and / or copper diffusion A method comprising the steps of: A is a phenyl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) , or a —CH—X—B group (wherein B has a phenyl group or 1 to 3 nitrogen atoms) A 5- or 6-membered heteroaryl group)
The method of claim 1, wherein The method according to claim 1, wherein X is a single bond, or a —CH ₂ — group or a —CH ₂ —CH ₂ — group. The method according to any one of claims 1 to 3, wherein Z is an amine group or a carboxyl group. Said diazonium salt carrying at least one functional group has the formula: N≡NDXZ
(Where
D is an aryl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) ;
X is a single bond or an alkylene group having 1 to 4 carbon atoms,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group)
A compound of
The method according to claim 1. The diazonium salt used in the first solution of step (A) b) has the formula: N≡NDXZ
(Where
D is an aryl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) ;
X is a single bond or an alkylene group having 1 to 4 carbon atoms,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group)
A compound of
The method according to claim 1. The method according to claim 5 or 6, wherein D is a phenyl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) . The method according to claim 5, wherein X is a single bond, a —CH ₂ — group or a —CH ₂ —CH ₂ — group. Z is an amine group or a carboxyl group, The method in any one of Claims 5-8. The compound carrying at least one functional group of the second solution is polysilazane.
The method of claim 6. The diazonium salt has the formula: N≡NDXZ
(Where
D is a phenyl group,
X is an alkylene group having 1 to 4 carbon atoms, and Z is a carboxyl group)
A diazonium salt of phenylalkanoic acid,
The method of claim 5. Said step of contacting said surface of said composite material with said solution comprises dipping, spraying or spin-coating said solution on said surface of said composite material;
The method according to claim 1. The multilayer composite device is a semiconductor device;
The method according to claim 1. A multilayer composite device obtained by the method according to claim 1. A composition for use in the method according to any one of claims 1-13,
A solvent,
Diazonium salt of aniline;
A diazonium salt carrying at least one functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group; or a precursor of a diazonium salt carrying said at least one functional group ; and <br/> _{formula: H 2 N-A-X} -Z
[Where:
A is an aryl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) , or a —CH—X—B group (wherein B is an aryl group or a heteroaryl group) . ,
X is a single bond or an alkylene group having 1 to 4 carbon atoms,
Z is a functional group selected from the group consisting of silane, silazane, siloxane, amine, hydroxyl group, and carboxyl group]
A composition comprising a solution containing at least one compound selected from the group consisting of: A is a phenyl group ( including those substituted with a hydroxyl group, a lower alkyl group or a halogen atom ) , or a —CH—X—B group (wherein B has a phenyl group or 1 to 3 nitrogen atoms) A 5- or 6-membered heteroaryl group)
Is,
The composition according to claim 15. X is a single bond or -CH ₂ - group or a _-CH 2 -CH ₂ - composition according to claim 15 or 16, which is a group. Z is an amine group or a carboxyl group, The composition in any one of Claims 15-17. In order to obtain a dielectric layer having a thickness of less than 15 nm,
The composition according to any one of claims 15 to 18. In order to obtain a dielectric layer having a thickness of 1 to 8 nm,
The composition according to any one of claims 15 to 18.